EP0747321A2 - Charbon actif granulé et son procédé de production - Google Patents
Charbon actif granulé et son procédé de production Download PDFInfo
- Publication number
- EP0747321A2 EP0747321A2 EP96108943A EP96108943A EP0747321A2 EP 0747321 A2 EP0747321 A2 EP 0747321A2 EP 96108943 A EP96108943 A EP 96108943A EP 96108943 A EP96108943 A EP 96108943A EP 0747321 A2 EP0747321 A2 EP 0747321A2
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- EP
- European Patent Office
- Prior art keywords
- active carbon
- granulated active
- carbon according
- reagent
- activation
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
- C01B32/384—Granulation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
Definitions
- the present invention relates to granulated active carbon and a process for its production. Particularly, it relates to granulated active carbon excellent in abrasion resistance during its handling and a process for its production.
- Active carbon is used in e.g. gasoline vapor collecting devices (canisters) mounted on automobiles, gas masks or deodorizing equipments in plants or laboratories, and it is used for various applications to adsorb and remove various contaminants in a gas phase, or adsorb and remove metals, etc. in a waste liquid.
- a reagent-activating method employing e.g. phosphoric acid or zinc chloride (Japanese Unexamined Patent Publications No. 146412/1991, No. 163020/1993 and No. 138010/1995).
- a wooden material such as a coconuts shell or wood, which is commonly used as a starting material
- a reagent having a carbon-activating function such as an aqueous phosphoric acid or zinc chloride solution
- the mixture is sufficiently impregnated and kneaded at a temperature of from room temperature to 200°C.
- a binder is added thereto to obtain a kneaded product, which is molded by e.g. granulation molding into granules having a particle size of from 0.35 to 10 mm.
- the granules are baked at a temperature of from 500 to 700°C to obtain active carbon activated by the reagent.
- the present inventors have conducted extensive studies to present a process for industrially advantageously obtaining granulated active carbon product which hardly undergoes degradation and which has a surface configuration excellent in abrasion resistance, as a process for producing granulated active carbon by a reagent-activating method.
- a process for producing granulated active carbon by a reagent-activating method As a result, it has been found that when molding of a kneaded product of the starting material for active carbon and an activating reagent, is conducted in the presence of a certain specific additive, the surface condition of the resulting granules will be good, and when such granules are baked, excellent granulated active carbon which hardly undergoes degradation can be obtained.
- the present invention has been accomplished on the basis of this discovery.
- the present inventors have conducted extensive studies also to present a process for industrially advantageously obtaining an active carbon product having low unit production cost by efficiently recovering and re-using the reagent used for activation and/or a compound formed by the activation reaction after activation treatment, as a process for producing active carbon by a reagent activating method.
- they have found an efficient process for recovering an unreacted activating reagent, etc. at a high concentration from the baked product after activation and recycling it for re-use, and a simple and effective means for controlling the concentration of the activating reagent.
- the present invention provides granulated active carbon having a specific surface area of from 60 to 3,000 m 2 /g as measured by a liquid nitrogen S-BET method (a multipoint method) and a degradation ratio of not higher than 1.5% as measured by a paint conditioner test method.
- the present invention provides a process for producing granulated active carbon as defined above, which comprises impregnating and kneading an activating reagent to a carbonaceous material to be activated by the reagent, to obtain a kneaded product, granulation-molding the kneaded product to obtain granules, and baking the granules to obtain active carbon, wherein the granulation molding is carried out in the presence of a polyhydric alcohol.
- the material which can be used as a starting material for active carbon in the present invention may be any material so long as it is a carbonaceous material which can be activated by a reagent.
- various carbonaceous materials are known, including, for example, as wooden materials, cellulose type such as chips of wood or coconuts shells, and starch type such as nuts, millet or corn.
- mineral materials such as peat and brown coal are also known.
- wooden materials, particularly cellulose materials are preferred, since the physical properties of active carbon thereby obtained will be particularly excellent.
- the size of such a starting material is not particularly limited. However, a particle size is preferably at most 5 mm, so that the material can readily be mixed with an activating agent and can readily be activated and molded.
- the activating reagent to be used in the present invention is not particularly limited so long as it is a reagent having an activating function. Any one of reagents which are commonly used for a so-called reagent-activating method, can be employed. For example, zinc chloride, calcium chloride, sodium hydroxide or phosphoric acid is suitable. Among them, zinc chloride or phosphoric acid is preferred, since the physical properties of the resulting active carbon will be particularly excellent. Further, a reagent known as a reagent having a dehydrating, oxidizing or corrosive property, such as potassium sulfide, sulfuric acid or various alkali materials, may also be used.
- the concentration and the amount of such an activating reagent may be suitably selected depending upon the type of the reagent or the amount of the starting material.
- phosphoric acid particularly orthophosphoric acid or paraphosphoric acid
- orthophosphoric acid is preferred, since the physical properties of active carbon thereby obtained will be particularly excellent.
- the concentration and the amount of such a phosphoric acid may be suitably selected depending upon the type of the reagent, the amount of the starting material, etc.
- these materials are usually charged into a mechanical mixing and kneading apparatus, such as a kneader, followed by kneading.
- the activating reagent and the carbonaceous material are kneaded for example at a temperature of from room temperature to 200°C, preferably from 100 to 180°C for from 5 minutes to 8 hours, preferably from 2 to 4 hours (initial kneading).
- a polyhydric alcohol which will be described hereinafter, is added thereto, followed by kneading, and such kneading after addition (final kneading) is carried out at a temperature of from room temperature to 200°C, preferably from 100 to 180°, within 30 minutes, preferably within 15 minutes.
- the activating reagent will be impregnated to the carbonaceous material.
- the kneaded product thus obtained is usually a dry powder.
- a binder In addition to the carbonaceous material and the activating reagent, a binder, etc., may be added as the case requires.
- a binder an organic binder such as sodium lignin sulfonate or a resin, or an inorganic binder such as bentonite or pitch, is known.
- the polyhydric alcohol which can be used may, for example, be a dihydric or higher alcohol such as glycerol, pentaerythritol, pinacol, 1,4-butanediol, 2-hydroxylmethyl-1,4-butanediol, polybutylene glycol, polyethylene glycol, polypropylene glycol or glycerol. Among them, polyethylene glycol, polypropylene glycol or glycerol, particularly glycerol, is preferred. As the valence of the alcohol, a trihydric or higher alcohol is preferred.
- the molecular weight is usually from 90 to 12,000, and the one having a molecular weight of from 90 to 1,000 exhibits particularly excellent effects.
- the polyhydric alcohol is used usually in an amount of from 1 to 50 wt%, preferably from 3 to 15 wt%, relative to the dry solid content in the blend proportion to the carbonaceous material. If the amount is too small, adequate effect for preventing degradation of the product intended by the present invention, is hardly obtained. On the other hand, if it is too much, the granules tend to adhere to one another, whereby the effect for preventing degradation of the product is likely to be inadequate. Further, the adsorption ability of the resulting active carbon is likely to be low.
- the timing for adding the polyhydric alcohol is not particularly limited, and it may simply be present together with the kneaded product of the carbonaceous material and the activating reagent during the granulation-molding.
- the effects of the present invention can be achieved, so long as the polyhydric alcohol is sufficiently dispersed. Accordingly, it may be added to the kneaded product or it may be added to the carbonaceous material and the activating reagent before the kneading. Otherwise, it is also possible to add the activating reagent to the carbonaceous material and then carry out the kneading while sequentially adding the binder and the polyhydric alcohol.
- the apparatus used for molding is not particularly limited, and an extrusion molding machine or a press molding machine is usually employed.
- a method of molding under heating to a temperature of from 50 to 100°C, or a method of molding at room temperature after cooling the kneaded product to the room temperature may, for example, be employed.
- heating is not particularly required, and the molding can be adequately carried out at room temperature.
- the resulting granules will be in the form of pellet-like granules having a diameter of from 0.35 to 10 mm in the case of extrusion molding.
- the molded product is pulverized into pulverized granules having a diameter of from 0.5 to 10 mm.
- the granules obtained by granulation-molding may preferably be subjected to a rolling operation prior to baking.
- the rolling operation may sufficiently be carried out, for example, by a trommel or a similar rolling apparatus, at a temperature of at most 100°C, usually from room temperature to 100°C, within two hours.
- the above granulated products are baked to obtain active carbon.
- the baking method is not particularly limited, and a conventional method may be employed.
- the baking is usually carried out by heating the granules to a maximum temperature of from 500 to 700°C.
- An equipment capable of controlling the gas atmosphere and carrying out the heat treatment such as a tunnel furnace or a rotary kiln, may be employed.
- the baked product After baking, the baked product is subjected to suspension washing with hot water in accordance with a conventional method, to remove the reagent used for activation, and then, dried.
- the suspension washing is carried out by suspending the baked product with water at a temperature of from room temperature to 100°C, leaving the suspension for from 5 minutes to 12 hours, preferably from 20 to 40 minutes, and then separating the product by filtration. This operation is repeated until the activating reagent is no longer detected from the filtrate.
- the drying is carried out usually at a temperature of at most 500°C, preferably from 100 to 150°C.
- the active carbon of the present invention has a specific surface area of from 600 to 3,000 m 2 /g as measured by a liquid nitrogen S-BET method (a multipoint method) and a degradation ratio of not higher than 1.5 % as measured by a paint conditioner test method.
- the degradation ratio as measured by a paint conditioner test method is determined in such a manner that a dry sample is put into a 140 ml mayonnaise bottle (made of hard glass with an inner diameter of 4.4 cm, a height of 9.5 cm and a wall thickness of 3 mm and having a metal cover), then, the bottle is fixed in a measuring apparatus, vibration is then exerted 10 7 times in an up and down direction under an acceleration of 3 G at an average of 40 Hz, whereupon the sample is shieved with a screen of 60 mesh, and the weight of the sample on the screen was measured to determine the amount of the sample passed through the screen, whereby the degradation ratio is represented by the weight % of the sample passed through the screen, relative to the total amount of the sample tested.
- the active carbon of the present invention can be made to have a specific surface area of from 1,500 to 2,500 m 2 /g as measured by a liquid nitrogen S-BET method (a multipoint method) or to have a degradation ratio of not higher than 1%, or it may be made to have the both physical properties simultaneously. Further, in addition to the above physical properties, the active carbon may be made to have an effective n-butane adsorptivity of at least 40 g/100 g. Namely, the active carbon of the present invention is a novel and highly valuable active carbon which has excellent properties such that the specific surface area is large, the adsorption performance is excellent, yet the degradation ratio is low, and the abrasion resistance is excellent, and which is useful for various applications.
- phosphoric acid used as the activating reagent
- the recovery method is not particularly limited.
- recovery by suspension washing which will be described hereinafter, is preferred, since such a recovery method is excellent in washing effects, and efficient washing can easily be carried out.
- suspension washing is carried out in such a manner that the above baked product is suspended and washed with water, preferably warm water, to remove the reagent used for activation, etc.
- the baked product is suspended in water in an amount of from 1.1 to 100 times by volume, preferably from 2 to 5 times by volume, relative to the baked product at a temperature of at most 100°C, usually from room temperature to 100°C, then left to stand for from 5 minutes to 12 hours, preferably from 20 to 40 minutes and then separated by filtration.
- the amount of water for suspension is too small, it tends to be difficult to separate water from the baked product which is a carbon material.
- the apparatus for treatment is obliged to be large, and the installation costs will be high. Further, the amount of treating water increases, and the phosphoric acid concentration in the recovered water decreases. Accordingly, the unit cost for production of active carbon increases, and such a process is inefficient. For such reasons, it is advisable to select the amount of water to be used, within the above-mentioned range.
- FIG. 2 shows a flow chart of the process for washing the baked product.
- the baked product from the first suspension washing is subjected to the second suspension washing, followed by the third, the fourth ... the n th suspension washing.
- the washing is repeated in this manner until the reagent or the like is no longer detected from the filtrate.
- a filtrate after washing will result each time, and this filtrate contains the activating reagent, etc.
- the concentration of the activating reagent decreases as n increases. Accordingly, it is preferred to countercurrently move the washing liquid and the baked product so that for the n th washing, the (n+1)th or subsequent filtrate is employed.
- either the filtrate or the baked product after washing may be moved.
- the filtrate obtained from the first suspension washing is concentrated by heating and may again be used for activation of active carbon.
- washing of active carbon can simply and sufficiently be carried out, and recovery of a phosphoric acid solution of a high concentration can efficiently be carried out.
- the filtrate obtained from the first suspension washing is concentrated in its entire amount without conducting suspension washing by means of the filtrate, the amount of the filtrate which must be concentrated by heating, will be as large as five times the case where such suspension washing is conducted. Accordingly, the size of the apparatus for concentration by heating is obliged to be large, and the operation cost will be about five times. Consequently, the unit cost for production of active carbon increases substantially, such being undesirable as a process for producing active carbon which must be competitive costwise. Further, the phosphorus compound formed by the activation reaction will react with water to form phosphoric acid. Accordingly, it is readily possible to recovery phosphoric acid from the baked product by washing the active carbon with water.
- the filtrate obtained by suspension washing of the baked product is put in a reactor made of a material having heat resistance and corrosion resistance against phosphoric acid, such as graphite, and heated while reducing the pressure by an equipment capable of efficiently reducing the pressure, such as a vacuum pump or an ejector, preferably an ejector, to evaporate water and concentrate the filtrate until the specific gravity of phosphoric acid becomes from 1.245 to 1.69, preferably from 1.332 to 1.582 at 15/4°C.
- a vacuum pump or an ejector preferably an ejector
- water or sea water of not higher than 40°C preferably water or sea water of from 0 to 5°C
- water evaporated from the aqueous phosphoric acid solution can be liquefied, and reduction of the pressure can be carried out efficiently, whereby the efficiency for concentration of the aqueous phosphoric acid solution can be increased.
- the water or sea water used in the ejector may be recycled for use or may not be recycled.
- the concentrated phosphoric acid solution thus obtained is re-used as an activating reagent.
- concentration control of the concentrated phosphoric acid solution by measurement of the specific gravity of the aqueous solution by means of a hydrometer, the concentration of the aqueous phosphoric acid solution can be detected very easily as compared with conventional methods such as a neutralization titration method of ammonium phosphomolybdate, a chelate titration method of ammonium magnesium phosphate, a potassium permanganate titration method of ammonium phosphomolybdate, a current titration method with uranyl acetate (Kolthoff-Cohn method) and a colorimetric analysis by reduction with stannous chloride, and production of active carbon by a reagent-activation method using phosphoric acid, can be carried out very efficiently.
- the active carbon is dried. This drying of the active carbon is conducted usually at a temperature of at most 500°C, preferably from 100 to 150°C.
- the concentration of phosphoric acid in the solution is low, and it takes a long treating time until granulation can be done after impregnation and kneading, and the size of the apparatus is obliged to be large, and the operation cost will be as high as about five times. Accordingly, the unit cost for production of the active carbon increases, such being undesirable as a process for producing active carbon which must be competitive costwise.
- Figure 1 the above described example of the process of the present invention is shown by a process flow chart.
- the unit cost for producing active carbon by the reagent activation method can be reduced, and active carbon highly competitive costwise, can be supplied efficiently on an industrial scale.
- the production ratio of fine powder after the abrasion test was shown in terms of a degradation ratio as measured by a paint conditioner test method.
- a measuring method is as follows.
- n-butane is one of gasoline vapor components
- the saturated effective adsorptivity of n-butane is regarded as a typical index for the gasoline vapor adsorption performance.
- the measuring method is as follows.
- the pellets were rolled for one hour by a trommel. After rolling, the pellets were baked by a rotary kiln of external heating system by supplying a gas mixture of hydrogen and air. Firstly, the temperature was raised from 100°C to 250°C at a rate of 12°C/min at an oxygen concentration of 0%. Then, the oxygen concentration was adjusted to 21%, and the temperature was raised from 250°C to 350°C over a period of two hours. Then, the oxygen concentration was adjusted to 4%, and the temperature was raised from 350°C to 550°C at a rate of 12°C/min. After the temperature reached 550°C, the baked product was immediately cooled.
- the baked product was suspended with water at 80°C, then left to stand for 30 minutes and separated by filtration. This operation from suspension washing to separation by filtration, was repeated five times, whereupon the activating reagent became no longer detectable from the filtrate. Then, the product was dried at 150°C.
- Example 2 The baked product obtained in Example 1 (Preparation of a baked product) was subjected to suspension washing in accordance with the flow chart shown in Figure 2.
- either the baked product or the filtrate may be moved to conduct the suspension washing of the baked product as a carbon material and the filtrate.
- the baked product was moved.
- the baked product was suspended with the filtrate from the second suspension washing at 80°C, left to stand for 30 minutes and then separated by filtration by means of a glass filter with a mesh not to pass the baked product. (First suspension washing)
- the baked product collected by filtration was suspended with the filtrate from the third suspension washing at 80°C, left to stand for 30 minutes and then separated by filtration by means of a glass filter with a mesh not to pass the baked product. (Second suspension washing)
- the baked product collected by filtration was suspended with the filtrate from the fourth suspension washing at 80°C, left to stand for 30 minutes and then separated by filtration by means of a glass filter with a mesh not to pass the baked product. (Third suspension washing)
- the baked product collected by filtration was suspended with the filtrate from the fifth suspension washing at 80°C, left to stand for 30 minutes and then separated by filtration by means of a glass filter with a mesh not to pass the baked product. (Fourth suspension washing)
- the baked product collected by filtration was suspended with water in an amount of two times by volume of the baked Product at 80°C, left to stand for 30 minutes and then separated by filtration by means of a glass filter having a mesh not to pass the baked product. (Sixth suspension washing)
- the baked product obtained by the sixth suspension washing was dried at 150°C to obtain active carbon.
- the filtrate from the first suspension washing in the above washing process was recovered and concentrated to a specific gravity of the aqueous solution of 1.69 while reducing the pressure by an aspirator. Then, phosphoric acid reagent was added afresh to make 2.0 kg of an aqueous phosphoric acid solution having a concentration of 85 wt%.
- the aqueous solution and 1.0 kg of a dried product of wood chips of at most 2.0 mm were subjected to kneading, baking, washing with water and drying treatments under the above-mentioned conditions.
- the active carbon obtained by using such regenerated phosphoric acid was of the same quality as the product obtained by using fresh phosphoric acid.
- the present invention in the process for producing granulated active carbon by a reagent-activation method, it is possible to obtain a product having a clean surface condition and being hardly degraded, on an industrial scale. Further, it is thereby possible obtain an inexpensive product efficiently on an industrial scale.
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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JP139458/95 | 1995-06-06 | ||
JP07139458A JP3092477B2 (ja) | 1995-06-06 | 1995-06-06 | 粒状活性炭及びその製造方法 |
JP7280727A JPH09118510A (ja) | 1995-10-27 | 1995-10-27 | 活性炭の製造方法 |
JP280727/95 | 1995-10-27 |
Publications (2)
Publication Number | Publication Date |
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EP0747321A2 true EP0747321A2 (fr) | 1996-12-11 |
EP0747321A3 EP0747321A3 (fr) | 1997-11-05 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP96108943A Ceased EP0747321A3 (fr) | 1995-06-06 | 1996-06-04 | Charbon actif granulé et son procédé de production |
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EP (1) | EP0747321A3 (fr) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001021306A1 (fr) * | 1999-09-21 | 2001-03-29 | Asahi Kasei Kabushiki Kaisha | Catalyseurs pour l'hydrogenation de l'acide carboxylique |
WO2009011590A1 (fr) * | 2007-07-19 | 2009-01-22 | Norit Nederland B.V. | Carbone activé chimiquement et ses procédés de préparation |
CN103785356A (zh) * | 2013-10-21 | 2014-05-14 | 溧阳市浙大产学研服务中心有限公司 | 一种用柚子皮、麻杆、核桃壳制备活性炭的方法 |
CN103787330A (zh) * | 2013-10-21 | 2014-05-14 | 溧阳市浙大产学研服务中心有限公司 | 一种用杏核壳、松塔、稻壳制备活性炭的方法 |
CN103816866A (zh) * | 2013-10-21 | 2014-05-28 | 溧阳市浙大产学研服务中心有限公司 | 一种用稻壳、玉米杆、椰子壳制备活性炭的方法 |
CN103818905A (zh) * | 2013-10-21 | 2014-05-28 | 溧阳市浙大产学研服务中心有限公司 | 一种用麻杆、核桃壳、梧桐树叶制备活性炭的方法 |
CN109748258A (zh) * | 2019-02-14 | 2019-05-14 | 安庆北化大科技园有限公司 | 一种生物质碳纳米复合微球材料及其制备方法和应用 |
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FR556686A (fr) * | 1922-09-29 | 1923-07-25 | Nouvel évaporateur | |
US3859421A (en) * | 1969-12-05 | 1975-01-07 | Edward E Hucke | Methods of producing carbonaceous bodies and the products thereof |
US3864277A (en) * | 1970-05-15 | 1975-02-04 | North American Carbon | Hard granular activated carbon and preparation from a carbonaceous material a binder and an inorganic activating agent |
US4155878A (en) * | 1978-05-10 | 1979-05-22 | Westvaco Corporation | Process for making activated carbon with control of metal ion concentration in phosphoric acid |
JPS5629162A (en) * | 1979-08-17 | 1981-03-23 | Sumitomo Bakelite Co Ltd | Filling agent for liquid chromatography |
EP0250382A2 (fr) * | 1986-06-19 | 1987-12-23 | Sandvik Aktiebolag | Echangeur de chaleur métallique utilisé dans le procédé à circulation forcée d'évaporation de l'acide phosphorique |
EP0423967A2 (fr) * | 1989-10-20 | 1991-04-24 | Norit (Uk) Limited | Procédé de fabrication de charbon actif granulé |
US5039651A (en) * | 1988-09-07 | 1991-08-13 | Takeda Chemical Industries, Ltd. | Chemically activated shaped carbon, process for producing same and use thereof |
EP0461802A2 (fr) * | 1990-06-12 | 1991-12-18 | The British Petroleum Company P.L.C. | Carbonylation du méthanol |
DE4234786A1 (de) * | 1992-10-15 | 1993-04-22 | Carbo Consult Ges Fuer Umwelt | Verfahren zur herstellung einer hochwertigen formaktivkohle aus lignozellulosehaltigen rohstoffen |
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JPS52153893A (en) * | 1976-06-16 | 1977-12-21 | Koa Oil Co Ltd | Manufacture of pelletized carbon |
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1996
- 1996-06-04 EP EP96108943A patent/EP0747321A3/fr not_active Ceased
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EP0423967A2 (fr) * | 1989-10-20 | 1991-04-24 | Norit (Uk) Limited | Procédé de fabrication de charbon actif granulé |
EP0461802A2 (fr) * | 1990-06-12 | 1991-12-18 | The British Petroleum Company P.L.C. | Carbonylation du méthanol |
DE4234786A1 (de) * | 1992-10-15 | 1993-04-22 | Carbo Consult Ges Fuer Umwelt | Verfahren zur herstellung einer hochwertigen formaktivkohle aus lignozellulosehaltigen rohstoffen |
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Title |
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CHEMICAL ABSTRACTS, vol. 88, no. 16, 17 April 1978 Columbus, Ohio, US; abstract no. 111080, NOGUCHI KOSAKU & AL.: "Granular activated carbon" XP002016363 & JP 52 153 893 A (KOA OIL CO.) 21 December 1977 * |
PATENT ABSTRACTS OF JAPAN vol. 005, no. 081 (P-063), 27 May 1981 & JP 56 029162 A (SUMITOMO BAKELITE CO LTD), 23 March 1981, * |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001021306A1 (fr) * | 1999-09-21 | 2001-03-29 | Asahi Kasei Kabushiki Kaisha | Catalyseurs pour l'hydrogenation de l'acide carboxylique |
US6495730B1 (en) | 1999-09-21 | 2002-12-17 | Asahi Kasei Kabushiki Kaisha | Catalysts for hydrogenation of carboxylic acid |
WO2009011590A1 (fr) * | 2007-07-19 | 2009-01-22 | Norit Nederland B.V. | Carbone activé chimiquement et ses procédés de préparation |
US8759253B2 (en) | 2007-07-19 | 2014-06-24 | Cabot Norit Nederland B.V. | Chemically activated carbon and methods for preparing same |
CN103785356A (zh) * | 2013-10-21 | 2014-05-14 | 溧阳市浙大产学研服务中心有限公司 | 一种用柚子皮、麻杆、核桃壳制备活性炭的方法 |
CN103787330A (zh) * | 2013-10-21 | 2014-05-14 | 溧阳市浙大产学研服务中心有限公司 | 一种用杏核壳、松塔、稻壳制备活性炭的方法 |
CN103816866A (zh) * | 2013-10-21 | 2014-05-28 | 溧阳市浙大产学研服务中心有限公司 | 一种用稻壳、玉米杆、椰子壳制备活性炭的方法 |
CN103818905A (zh) * | 2013-10-21 | 2014-05-28 | 溧阳市浙大产学研服务中心有限公司 | 一种用麻杆、核桃壳、梧桐树叶制备活性炭的方法 |
CN103787330B (zh) * | 2013-10-21 | 2015-08-05 | 溧阳市浙大产学研服务中心有限公司 | 一种用杏核壳、松塔、稻壳制备活性炭的方法 |
CN103785356B (zh) * | 2013-10-21 | 2015-09-23 | 溧阳市浙大产学研服务中心有限公司 | 一种用柚子皮、麻杆、核桃壳制备活性炭的方法 |
CN109748258A (zh) * | 2019-02-14 | 2019-05-14 | 安庆北化大科技园有限公司 | 一种生物质碳纳米复合微球材料及其制备方法和应用 |
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